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CHEMICAL SCIENCES (NET-JRF/GATE)

Unit Test: Organometallic Compounds

Time : 01:00 Hour

M.M. : 50

Instructions:
1.
Question Paper contains 25 objective type questions, each question carry 2 marks.
2.
There is nagative marking, 0.5 mark will be deducted for each wrong answer.
3.
Attempt all the questions, use of calculator is not allowed.
1.

Consider the metal carbonyl complex (A)

M CO 6
where q = 2, 1, 0, +1

The strongest CO band in IR spectrum can be observed when the value of q will be
(a) 2
(b) 1
(c) 0
(d) +1
2.

Arrange the following compounds inorder of their increasing ligand substitution rate of CO with phosphine.

Re
CO

OC
OC

(A)

(a) A > B > C

(b) B > C > A

Re
OC
CO OC

(B)

(c) C > A > B

Re
CO

OC
OC

(C)

(d) C > B > A

3.

When Co2(CO)8 reacts with CHCl3, yields compound (A) with molecular formula Co3C10HO9. Both IR and
NMR data indicate the presence of only terminal CO ligand and the structure is symmetrical on the basis of
above information which of the following statement about the structure (A) is not correct.
(a) The compound (A) follows 18 electron rule.
(b) The number of per MM and total number of MM bonds are 3 and 2 respectively.
(c) The oxidation state of the metal Co in product (A) is +1
(d) It has a carbido ligand which present in 3 bonding mode.

4.

In the reaction given below

PEt3
Ir CO Cl PPh 3 2
P

The major product P and their respective mechanism for the formation of product are

(a) Ir CO Cl PPh 3 PEt 3 PPh 3 , dissociative.

(b) Ir CO Cl PPh 3 PEt 3 PPh 3 , associative
(c) Ir PPh 3 2 Cl PEt 3 CO, associative.
(d) Ir PPh 3 2 Cl PEt 3 CO, dissociative.
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5.

When TiCl4 is treated with EtMgBr at low temperature it forms a compound (A), and the compound (A) is
unstable at above 70C however, when TiCl4 is treated with LiCH2SiMe3 it forms a compound (B) and the
compound (B) is stable even at room temperature, this is due to
(a) The compound (A) is formed by the action of Grignard reagent, and the said reagent is unstable at high
temperature.
(b) The compound (B) is formed by the action of organolithium reagent, and the said reagent is stable even at
high temperture.
(c) The compound (A) undergoes -elimination therefore the said compound is unstable at high temperature.
(d) The compound (A) undergoes -elimination at high temperature where as, in compound (B) there is no
chance for -elimination even at low and high temperature.

6.

5 CpFe CO (A) is a dark green solid compound. The IR spectrum shows a single CO stretching band
4
1
at 1640 cm . The 1H NMR spectrum shows a single line even at low temperature. Which of the following
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statement is not true on the basis of gien data about the structure of CpFe CO 4
(a) The complex (A) follows the 18 electron rule.
(b) The total number of MM bonds in complex are six.
(c) All COs are present 3 -mode.
(d) Two COs are present in 2-mode where as another two COs are present at 3 modes.
7.

Arrange the following in increasing order of C C for the following complex

+

F2

OC CH2

OC

F2

(A)

(B)

CH2

CO

CO

(a) B < D < A < C

8.

2+

CH2

CO

(b) C < A < D < B

2+

CF2

CO
OC CH2

OC CF2

(C)

(D)

(c) B < A < D < C

(d) A < B < C < D

Indenyl is a well know organometallic ligand the structure of indenyl ligand is

the haptacity and

electron contribution for the indenyl complex [(Indenyl)Fe(Cp)(CO)2] are respectively.

(a) 1, 1
(b) 3, 1
(c) 1, 3
(d) 1, 0
9.

Arrange the following inorder of their increasing CO stretching frequency..

(2) Mn CO 6
(3) Cr CO 6
(4) V CO 6
(5) Ti CO 6
(a) 5 < 4 < 3 < 1 < 2 (b) 5 < 4 < 3 < 2 < 1 (c) 2 < 1 < 3 < 4 < 5 (d) 1 < 2 < 3 < 4 < 5
(1) CO

10.

The cluster Co 6 CO 15 , Fe5 CO 15 C and Ni5 CO 10 having the structure respectively..

(a) closo, arachno, nido
(b) nido, arachno, closo
(c) closo, nido, arachno
(d) closo, closo, nido

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11.

Ferrocene undergoes electrophilic substitution reaction such as Friedel-Crafts acylation reaction with MeCOCl/
AlCl3 to give mixture of products the major product have following spectral characteristic
1
H NMR: In 1H NMR the major product gives 4 signals at value 2.8, 4.78, 4.4 and 4.2 (in ppm).
13
C NMR: In 13C NMR it gives six signals.
On the basis of above information identify the major product.
O

O
CH3

(a)

Fe

(b)

Fe

CH3

(c)

Fe

Fe

O
CH3

(d)

CH3

CH3
O

12.

Arrange the following metallocene inorder of their increasing ML bond length (where L = Cp)
+
(A) Cp2Fe
(B) Cp2CO
(C) Cp2Ni
(D) Cp Fe
2
(a) A < D < C < B
(b) B < C < D < A
(c) A < D < B < C
(d) C < B < D < A
R

13.

R
R

M
(B)

(A)

Which one of the following statement is correct about the structure (A) and (B).
(a) The structure (A) is favourable when the M present in the high oxidation state such as Pd(+2), Hg(+2).
(b) The structure (B) is favoured when the M present is low oxidation state such as Pd(0) and Hg(0)
(c) The structure (A) is favoured when the M present in low oxidation state such as Pd(0), Hg(0) and R may
be electron releasing group such as (CH3)
(d) The structure (B) is favoured when the M present in high oxidation state such as Pd(+2), Hg(+2) and R
may be electron releasing group.
14.

1.H 2O
Mn CO 6
P
2.
The major product P in the above reaction is

(a) Mn CO 6 H 2 O
(c) Mn CO 6 H

(b) CO 5 Mn COOH

(d) H Mn CO 5

(1)
(A)
Mo

15.
(3)

(2)

(4)

The compound (A) can undergoes nucleophilic addition at position 1, 2, 3 and 4. This addition of nucleophile
on alkene is possible due to umpolung effect the rate of nucleophilic attack will be fastest at position.
(a) 4
(b) 2
(c) 1
(d) 3

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16.

Consider the following statements

(A) H2 addition on Wilkinsons catalyst leads to dissociation of one of the PPh3 ligand to give a site at which the
alkene binds because the trans effect of PPh3 is greater than H.
(B) The selectivity for different alkenes for hydrogenation of alkene follows the order
monosubstituted > disubstituted > trisubstituted > tetrasubstituted
H

OH

H2/wc

(C)

H
O
MeO
NHCOMe

[(BINAP)(Rh)(PPh3)Cl]

(D) AcO

P(Pain killer)
naproxen

CO2Me

This is an example of asymmetric hydrogenation of alkene.

R

(E)

CO
R
H2
Co2(CO)8

H
O

The active form of the catalyst for this reaction is HCo CO 4

The correct statements is/are
(a) E, D only
(b) All
17.

(c) B, D, E

(d) A, B, C and D only

Using the M.O. diagram of Re 2 Cl8 the bond order of following cluster
Mo 2 O 2 CCH 3 4 , W2 Cl 4 PMe3 4 , Mo 2 CH 2SiMe3 6 will be respectively
(a) 3, 3, 4
(b) 3, 4, 3
(c) 4, 4, 3
(d) 4, 4, 4

18.

The colour of Re 2 Cl8

arries due to

(a) d d transition

(b) * transition

(c) * transition

(d) * transition
Br

19.

C6H13

+
O

1.

(B)

(A)

2. H2O

Pd(PPh3)2Cl2
KOH
toluene

The major product (B) in the above organic transformation is

(a) C6H13

(b) C6H13

C6H13

(d) C6H13

(c)

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Ph

PhI

20.

Pd(PPh3)2(OAc)2
HCOOH, R2NH, DMF

The above synthetic transformation is an example of

(a) Suzuki reaction
(b) Stille reaction
(c) Sonogashira coupling reaction
(d) Heck reaction
CH2
PMe3

21.

Cp2Ti

H2C

CH2

PMe3

Cp2Ti

CH2
PMe3

Which of the following statement is not true regarding the above reaction.
(a) The metal undergoes ligand substitution reaction by dissociation mechanism
(b) During the reaction (reactant product) the electron count and oxidation state of the metal has not been
charged.
(c) The CC bond length is larger in the reaction than that of product.
(d) In product, the ligand ethylene is present in 2 mode and formal charge contribution is zero.
22.

Consider the catalytic reaction mechanism

H3C

H3C

H3C
H

H2

CH3

Pd(0)

(A)
H

(D)

Pd
H

CH3

H3C

CH3

H3C
H3C

CH3
H

H3C

CH3

Pd
H

(C)

(B)
H3C

CH3

H3C

CH3
H

Pd

The mechanistic step involved in the above reaction is:

(a) A= oxidative addition, B = insertion, C = RE, D = co-ordination
(b) A= OA, B = co-ordination, C = insertion, D = RE
(c) A = RE, B = MI, C = -elimination, D = -elimination
(d) A= alkene co-ordination, B = -elimination, C = MI, D = RE.

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23.

Consider the compound (C8H8)Ru(CO)3. Which is likely to be the best description of the C8H8 ligand.
(a) It is bonded in an 8-manner to the Ru atom and one 1H NMR signal is observed over a range of temperatures.
(b) It is bonded in an 4-manner to the Ru atom, but one 1H NMR signal is observed in the limiting high
temperature spectrum.
(c) It is bonded in an 3-manner to the Ru atom and the 1H NMR spectrum is consistent with a stereochemically
non-rigid molecule.
(d) It is bonded in an 3-manner to the Ru atom and the 1H NMR spectrum is consistent with a static structure.

24.

The reaction of (6C7H8)Mo(CO)3 with [Ph3C][BF4] results in:

(a) proton abstraction and formation of [(7C7H7)Mo(CO)3]
(b) proton abstraction and formation of [(5C7H7)Mo(CO)3]
(c) hydride abstraction and formation of [(5C7H7)Mo(CO)3]+
(d) hydride abstraction and formation of [(7C7H7)Mo(CO)3]+

25.

Which statement is incorrect about CO ligands.

(a) A CO ligands can accept electrons into its * MO; this weakens the CO bond.
(b) In the IR spectrum of Fe(CO)5, absorption assigned to the CO stretching modes are at higher wave
number than that of free CO.
(c) CO ligands can adopt terminal, and 3 bonding modes; the amount of back donation depends on the
bonding mode.
(d) Fluxional behaviour is common in metal carbonyl compounds, and can be investigated by 13C NMR
spectroscopy.

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CHEMICAL SCIENCES (NET-JRF/GATE)

Unit Test: Organometallic Compounds

[ANSWERS]

1. (d)

2. (d)

3. (b)

4. (b)

5. (d)

6. (d)

7. (a)

8. (a)

9. (b)

10. (c)

11. (c)

12. (c)

13. (d)

14. (d)

15. (d)

16. (c)

17. (c)

18. (c)

19. (c)

20. (d)

21. (c)

22. (b)

23. (b)

24. (d)

25. (b)

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